Treatment of textile material and product thereof



Patented July 11,1939

- UNITED STATES manual-or PATENT-t OFFICE 'rnxmn rnonoc'r manormn Lilienfeld, Vienna, Austria n6 1mm. Application June 22, 1932, Serial No. 818,804.. Renewed m n 15, 1938. In Great Britain July 4, m1

I locu (01. 91-68) The present invention relates to a process of treating textile material (whether in the form of woven fabrics or spun goods such as yarn) by coating, impregnating, filling, dressing, weight- 5 ing, sizing, printing or the like by means of cellulose'or of cellulose derivatives or of cellulose compounds. It is based on the discovery that the textile materials attain excellent properties when the cellulose .or its derivatives or compounds are deposited on, or in the fibers of the textile ma;-

terial from a lather into which a solution of cellulose or of a cellulose-derivative or a cellulose by solution of the gas in the liquid under pressure or by dissolving a gas-liberating salt such as sodium carbonate, in such solution) and thereafter treating the material to regenerate or precipitate the cellulose, so as to produce a composite' material comprising fibrous material associated. with a dressing or sizing of regeneratedcellulose containing hollow spaces or bubbles dispersed throughout it or throughout a part of it. A convenient way of obtaining the solution from which cellulose may be regenerated or pre- 1 cipitated consists for example in injecting-air or another gas into a viscose so as to produce an emulsion of gas bubbles in the viscose. There:

may be added to the viscose or cellulose solution 40 various other substances, for'instance softening agents such as 'glycerine, soap, Turkey-redoil, glucose, castor oil or parafiin oil.

I have now-'found that the application of the solution .of paste of cellulosic material, in the form of a lather, (instead of emulsion) in acfore applying the same to the textile material, in

such a manner as to convert it into a lather.

A The advantageous properties of the coatings fifi coverings, dressings, fillings, sinings, printings,

and finishings made according to the present in-' "vention are, for example, their attractive appearance, their pleasant, warm and rich feel to the touch, their great voluminosity, their downy character and very-low specific gravity. In all 5 these'respects the final products of the present invention surpass the products obtainable ac- .cording to the known processes (as in my said prior patents) of incorporating'with textile materials cellulose or cellulose compounds in the 10 form, of coatings, dressings, sizings, fillings, weighting materials or printing layers which contain hollow spaces produced by emulsions of air or any other gas in solutions or pastes of cellulose or cellulose conversion products or'cellulose 15 compounds. The characteristic feature of the present invention-the lathery condition of the solutions or pastes-being absent in the emulsions I prepared according to the processes known heretofore, the volnminosity, specific gravity, soit- 20 ness and feel of the final products made according to the known processes are distinctly inferior to the voluminosity; softness, feel and specific gravity of the final products of; the present invention. The capability of the invention of im- '26 parting the greatest possible -volume to its initial materials (that is to say, to the solutions or ,pastes of cellulose or of its conversion products or derivatives) and,-what is more important, to

7 its final products, appears to be unrivalled in its 30 domain of application.

To show that the apparent specific gravity of the cellulose or of the cellulose derivative deposited on, orin, the textile fibre in thepresent invention is almost incredibly lower than the 35 apparent specific gravity of the cellulose deposited on, or in, the fibre in the processes in which emulsions (as in Patent 1,829,905) of. a gas in viscose or cellulose solutions are used, I

adducethe following example: Whilst the ap- 40 parent specific gravity of cellulose regenerated from viscose in, or on, the fibre is about 1.5 to 1.6, and whilst the apparent specific gravity of the cellulose deposited in, or .on, the fibre from an emulsion of a gas in viscose (for example ac- .45 cording to the process described in my U. S. Patent- 1,829,905) is, at theoutside, 1.2 to 1.3, according to the presentinvention itis possible to reduce the apparent specific gravity of the cellulose regenerated from viscose far below 1.2 and even down to 0.5 or even down to 0.1 to 0.2. This fact alone proves that, from the viewpoint of economy and, what is more important, with regard to lightness, softness and downy character of the dressings and sizlngs, the advantages of '65 the present process over all known processes in which cellulosic bodies by themselves or associ-.

,ated with hollow spaces are deposited within texlathery condition, the cellulose or the cellulose compound or cellulose derivative associated with the textile material according to the present invention is so intimately amalgamated with the textile fibre that the fastness towards rubbing, or bending or laundering of the final products is even then highly remarkable'even when unusually large amounts of mineral fillers (for example talc or china clay) are incorporated with the lather or the solution or paste to be transformed into'lather. Y

A suitable solution of cellulose, for example in cuprammonia solution, or in a zinc chloride solution, or in a mixture of caustic alkali solution with guanidine or with urea or thiourea or another suitable member of the group of ammonia derivatives of CO2 or CS2, or in a solution of a thiocyanate, for example calcium thiocyanate, or a suitable solution of a conversion or oxidation or degradation product of cellulose, or of mercerized cellulose, in short 01 any of the ,cellulosic materials proposed for being employed in the industry of solutions of cellulose, or of a suitable cellulose derivative, such as a suitable cellulose ester of lower stage of esterification, or

-of a-suitable cellulose ether, for example ethyl cellulose or methyl cellulose of a low degree of etherification, or of a suitable N-substituted thiourethane of cellulose, for example a 'phenyl thiourethane of cellulose, or of cellulose xanthate (viscose)- -which expression ,is intended to include xanthates of cellulose or of its conversion degradationor oxidation-products, in short of all cellulosic materials that have been proposed as parent materials for the manufacture of cellulose xanthate, (viscose) or 'of other cellulose derivatives-or of another suitable cellulose derivative containing a CSS-group, for instance of a cellulose xantho-fatty acid, or of a product resulting from contacting a cellulose xanthate (or a xanthate of another cellulosic body or another cellulosic compound containing a 055-.

group) with a halogen derivative of a dior polyhydric alcohol (e. g. a chlorhydrin), as covered in my Patent No. 2,021,862, or with one 'or more of the reagents (e. g. halogen fatty acids or their salts or esters) set forth in my Patent 2,087,981,

or with one or more of the reagents (e. g. halogen derivatives of sulphur derivatives of dior polyhydric alcohols) set forth in my U. S. Patent 2,100,968, or with one or more of the reagents (water-soluble organic bodies which contain halogen, nitrogen and hydroxyl, all linked to carbon atoms in' an aliphatic nucleus), or a solution of a xanthated derivative of an alkyl or aralkyl or hydroxy-alkyl ether of a cellulosic body as described in my U. S. Patents 1,858,097 or 2,021,861 or 1,910,440, or 2,100,010 or my British Patents 357,167 or 357,527 or 368,288, all can be used in the form of a paste (or preferably a solution) as the parent material for production of the lather.

The solution or paste of the cellulosic body may be transformed into a lather by mechanical means, for example by violet agitation or beating of the solution or paste orby blowing into, or

. through, the solution or paste a veryviolent current of air or of another gas, in short by any one of the well-known methods for producing lather or foam. The experience gained hitherto has however taught me that it is very diflicult and in many cases even impossible, by purely mechanical means, to transform the solutions or pastes in question into so stiff,- voluminous and stable a lather as they yield when substances capable of creating lather such as bodies belonging to the group of saponins, for example saponin-quillajin (quillaja-saponin), githagin (saponin of agrostemm'a githago) or the like, proteins, degradation products of the latter such as peptones or albumoses, soaps, solvenol (sodium salt of benzyl sulphanilic acid) in the presence or absence of sodium carbonate, monopol oil, Turkey red oil, monopol soap (a well known sulphonated castor oil soap) dyestuffs capable of creating lather or the like are used in conjunction with suitable mechanical means.

It must be borne in mind that the really lathery condition of the solutions or pastes being not only characteristic of the present invention, but also the sole factorresponsible for the new effect of the present invention, that is for the superior voluminosity, specific gravity, softness, feel and the like of the final products of the present invention, a thorough transformation into a lather and a more or less stiff condition of the lather is essential. the transformation of the solutions or pastes into a lather by 'means of substances capable of creating lather in combination with effective mechanical means which by themselves in no case give results thatare to be compared with the results obtained in presence of lather creators. I also prefer to conduct the transformation of the solutions or pastes 'into lather in such a manner'that the lather attains a certain stiffness and retains its lathery condition, stiffness and voluminosity for a longer time.

Since in a lather the fluid is only the dispersion medium, the dispersed phase being a gas, a" gas must be present when the solution or paste is transformed into lather. I prefer to use for this purpose air, but, 'if desired, any' other gas, such as nitrogen or hydrogen or carbon dioxide may be used.

All .the details of the practical carrying out of the second phase of the invention, that is the application of the lather to the textile material, for example the mechanical part of the process,

, or the precipitating baths, or the washing meth- -vention, in all cases in which solutions of cellulose or solutions of such conversion products or derivatives of cellulose'are used as are insoluble in water or organic, volatile solvents, the cellulose or the conversion products of cellulose or the cellulose derivatives mustbe precipitated 'or regenerated by meansof suitable precipitating or coagulating agents, which, if desired,-may also lated material.

I note that in my U. S. Patent 1,829,904 and inmy [7.6. application 367,155, filed May 29. 1929 (and in a substitute application 51,171 filed In consequence, I prefer to perform .70 exert a plasticising action on the freshly coagu- Nov. 22, 1935) I have described the application to textile materials of viscose containing. gas -in solution or in the form of The disclosure of said patent may serve as a guide with respect to the details of the cloth-finishing art.

I shall now give several examples of my invention. but it ,will be understcddthatthe invention is not limited to these details. Consequently, many variations may be made therein without departing from the spirit of the invention; The parts'are by weight:- 1

I Example 1 to (d) (a) 18 parts of Marseilles soap dissolved, in 720 parts of water are addedto 1428 parts of a viscose taining about 6.5 per lose and 8 per cent.

prepared from 100 parts ofcellulose and codcent. of precipitatablecelluof caustic soda. The mixture is filtered two to I v nated once or (optionally withintermediat drying) several times in a backfilling or padding machine with the lather thus produced.

In either case this is not merely a surface coating but there is a substantial penetration of the substance of the latherinto the fabric, 1. e. the fabric is impregnated.

Then the dressed material, in the wet state or is introduced into any after intermediate drying, precipitating bath known in the viscose art, such as the so-called Mueller-bath, for instance a bath containing per litre-160 Instead of a precipitating bath that has only. onthe viscose, a so-called a coagulating effect salts, or of organic substances. K

The Lilienfeld-p'rocess can also be employed in" a two-bath system in which case the impregnated material is first introduced into a bath that has only a coagulating eflect on the viscose 'and then "into a bath that has a plasticising efiect on' the freshly coagulated viscose.

As far as viscose is concerned, all baths known in the viscose art and/or in the art' of making artificial materialls, particularly threads from any alkali-soluble derivatives or conversion products and from alkaline. cellulose solutions are meant to be included in the expression coagulating baths? gar-coagulating agents? whereever this expression is used to define such baths .as have little or no plasticising effect on the freshly coagulated only the so-called' material, 1 Consequently, not

' cation thereof come into consideration as coagulating baths in the present process, but all baths known in the. viscose art regardless of whether .per cent. strength is t acidsalts, such'as bisulphates, for instance ammonium bisulphate, or

' mixed withone or acid salt, such as such as glucose, or an alcohol, or

Mueller bath or any modifi or not, in addition to the purely-coagulating constituents, such as acids and/or acid or neutral salts, they contain any other inorganic or organic (liquid, oily, crystalline or colloidal) substance or substances.

. As far as piasticising baths are concerned, particularly suitable are by itself or in admixture with one or more other organic ,or one or more inorganic. substances, a

large propor dies: Acid esters formed from a polyhydricaliphatic on of oneor more or the following (for example oxy- (hydroxy hmethylsulphonic acid. or methionic acid or methylor ethylsulphonic acid or a mineral oil orbehzene-sulphonicacid or phenol-,p

admixture with sulsulphonimacidby itself or in phuric acid), or

Carboxy-organo-nnneral acids (for example sulphono-di-acetic acid or sulpho-acetic acid by itself or in admixture with sulphuric acid), or

poiybasic inorganic" Aromatic suipho-acids containing nitrogen by themselves or in admixture with sulphuric acid, or v i Baths in which sulphuric acid of less than 55 used in combination with Strong sulphuric acid containing formaldehyde or pyridine or another organicsubstance, or

Solutions-of zinc halides alone or mixedwith anacid or with another salt or both, or

Any other'plasticising'agent or equivalent for strong mineral acid. i v l The strong sulphuric acid ,or other mineral acids or other plasticising agents mentioned above may be used alone or (so -far as isin organic substances, such as glycerme, or a sugar; a salt of an organic base,'f0r instance an-aniline salt, or pyridine, or a pyridine salt, or an aldehyde, or an organic acid,

such as acetic acid,'or formic ac'icL.

or lactic acid, or oxalic acid. 4 y In the impregnated materia the cellulose may also be regenerated by other methods, for example by steaming or heating the material, or by allowing the coated or impregnated textile material to remain at room temperature until the regeneration of the cellulose occurs.

The material is washed, dried and finished in the usual manner.

It will be understood that the material may be desulphurised or bleached in any known manner before or after it has been dried.

(b) The process is conducted as in (a), but with the difierence that only 5 parts of Marseilles soap are used.

The process is conducted as in (a), but with the difference that 50 to '70 parts -.of Mar seilles soap are used.

((1) The process is conducted as in (a) or (b) or (C), but with the difierence that, instead of Marseilles soap, another soap, for example ordinary shaving soap, or monopol soap, or solvenol and sodium carbonate, or monopol oil, or Turkey red oil, or a mixture of Turkey red oil and soap, or a peptone, or an albumose, or albumen, or saponin is used.

Example 2 ,(a) to (a) The process is conducted as in any one of the Examples 1 (a) to (d), but with the difference that to 300 per cent. (calculated on the cellulose contained in the viscose) of French chalk or china clay are added to the viscose before or afterit has been transformed into lather.

Example 3 (a) to (d) Mode of procedure as in any one of the Examples 1 (a) to (d), but with the difierence that the initial viscose contains 8.26 per cent. of precipitable cellulose and 9.4 per cent. of caustic soda solution and that the substance creating lather is dissolved in 300 parts of'water. The volume of the final lather is about-three times as large as the volume of the viscose before it has been transformed into the lather.

Example 4 (a) to (d) Mode of procedure as in any one of the Examples'3 (a) to (d), but with the difference that, instead of 18 parts, 5 parts of Marseilles soap are used. The volume of the final lather is about three and a half times as largeas the volume of the viscose before it has been transformed into the lather.

Example 5 (a) to (d). The process is conducted as in any one of the -Examples 3 (a) to (d), but with the difierence that the initial viscose contains 8.26 per cent. of cellulose and 5.9 per cent. of caustic soda.

Example 6 (a) to ((1) Mode of procedure as in' any one of the Ex-' amples 3 (a) to (d), but with the difierence that the initial viscose contains 8.26 per cent. of cellulose and 3.8 per cent. of caustic soda.

r Example 7 (alto (d) The process is conducted as in any one of the Examples 1 (a) to (d), but with the difierence that the viscose is prepared from a. very viscous cellulose rich in alpha-cellulose (for instance from very viscous cotton linters or the so-called alpha-fibre cellulose), creating lather is dissolved in 1905 parts of caus-' tic soda solution of 2.7 per cent. strength.

Example 8 (a) to ((1') Mode of procedure as in any one of the Ex- -tions to 100 parts of cellulose placed in or in 1940 parts and that the substance No. 1,674,401) dissolved and caustic soda corresponding with the proportions contained in the viscoses employed" amples 'l (a) to (d), but'with the difierence that the initial viscose contains 7 per cent. of precipitable cellulose and 11.3 per cent. of caustic soda solution and that 5 parts of Marseilles soap dissolved in 1905 parts of water are added.

Example 9 (a) to (a) to (d), but with the difierthe viscose is prepared from an alkali cellulose that has been allowed to mature for a long time, say 96 to hours), and that the substance creating lather is dissolved either in 714 parts of water or in 714 parts of caustic soda solution of 3 per cent. strength.

Example 10 (a) to .(d)

Mode of procedure as in any of the Examples 1 (a) to (d), but with the difference that the initial viscose contains 8 per cent. of cellulose and 12 per cent. of caustic soda, and that the substance creating parts of water.

lather is dissolved in 750 Example 1 1 10 per cent; of one of the substances creating lather set forth in Example 1, in 1068 parts of water, or in 1668 parts of a caustic soda solution of 2.8 per cent. strength, or in 1068 parts of caustic soda solution of 6.5 per cent. strength or in 2973 parts of caustic soda solution of 4.2

per cent. strength.

The lather thus obtained is employed for impregnating cloth according to Example 1.

Example 12 400 to 600 parts of .caustic soda solution of 20 per cent. strength are added in small pora shredder or a vacuum xanthate machine of Werner and Pfleidererand the mass kneaded or shredded respectively until homogeneous, whereupon 60 parts of carbon bisulphide are added and the kneading is continued for another 2 to 3 hours.

"After that time, the excess carbon bisulphide is blown ofi and 5 to 50 parts of one of the substances oreating lather set forth in Example 1 and dissolved in 668 parts of water, -or in 868 parts of water, or in 1240 parts of water, or in 1440 parts of water, or in 1740 parts of water, of caustic soda solution of 2.3 per cent. strength, are added to the viscose whereupon the mixture thusobtained is brought into alathery condition as described in Example 1 and then used for'impregnating a cotton fabric according to the prescription given in Example 1.

Example 13 6 The process is conducted as in any one of the preceding examples, but with the difference that,

instead of viscose, a solution of a phenylithio urethane of cellulose (for example prepared ac described in my Patent" in a 'proportionofsiwater I cording to the process containing about 100 parts -context permits, any spun .or'w'oven textile material, whether animal orvegetable (for example, fiax, linen, hemp, ramie, jute, wool, and particuin the foregoing examples is used as initial material.

Erample 14 The process is conducted as in any one, of 'the preceding examples, but with the difierence, that, instead .of being introduced into a coagulating or coagulating and plasticising bath, the impregnated material is dried and thereafter steamed The process is conducted as in any one of the" foregoing examples,but with the difference that the impregnated material is, at any stage of manufacture subsequent to the coagulating step,

introduced into. a solution of a shrinking agent,

for example into a caustic soda solution of 7 percent. strength, or into a caustic soda solution of 22 per cent. strength and thenwashed and dried.

Instead of viscose, a solution of cellulose or of a conversion product of cellulose in cuprammonia orcaustic soda solution containing thiourea or guanidine (see my U. S.patent.No. 1,771,460 and No, 1,771,461), or in calcium thiocyanate can be used in the present invention.-

' Also solutions onpastes, of cellulose esters, such as cellulose acetate or cellulosnitrate or of cellulose ethers, such. as ethyl ormethyl ether of cellulose of low degree of etherification can be brought into a lathery condition by means of the described methods and the lather employed as a coating.

, Example 16 v The process is conducted as in any one of the Examples 1 to 15, but with the difference that 10 to 30 parts (calculated on the cellulose. contained in the viscose) of'B-dichlor'ohydrine, o r monochlorohydrine, or ethylene chlorohydrine, or- 20 to 50 parts of' one of the products described, or mentioned in my U. S. Patent 2,100,968 or used in my U. S. application Ser. No. 597,640 respectively, or 20 parts of a-dichlorohydrine and 20 parts of one of the productsdescribed or nientione'd inmy U s. Patent 2,100,968or used in my co-pending U. S. application Ser. No. 597,640 respectively, or20 parts-of a-dichlorohydrine and .20 to 50' parts of one of the products. described or mentioned in my British Patents 390,516 or 390,523 or usedin my U. S. Patent 2,051,051 respectively, or 20 to 30fpaits of oneor more reagents belonging to the group set forth in my U. S. Patent 2,021,864 are added to the viscose.

The expression cellulose" is, wherever the context permits," intended to'denote not only cellulose, but also its c nversion products, for example its hydrates or degradation 'products or oxidation products.-

It is to'be understood that in the -following claims the term fapplying to textile material" includes any manner of application to the textile material, whether by manual or mechanical means customary for dressing, sizing, filling, impregnatiuE-coating, weighting or printing textile material, whether in the state of woven fabrlcs, or in the state. of yarn.

The term lather as used in and claims is not to be limited to a foam' or froth produced only by reason of the presengeof soap or its equivalent.

The expression textile m'ateriaP'in the speci fication and the claims includes, wherever the the solution the specification larly cotton) as well as artificial fibres of any kind in the form of yarn, staple fibre or fabrics consisting of or containing artificial fibres, in the form of pure fabrics, or in the form of mixed fabrics, or in the form of yarn inskeinsfcops or warps. I

The invention embraces the production of coatings, impregnations and layers of every kind generated cellulose, and regenerated cellulose derivatives or compounds, including those produced by coagulating and/or plasticizing from the solu-.

tions or pastes described above. The term solution of a xanthate of acellulosic compound is intended to cover viscose and the products made.

by contacting viscose with an'organic substance, .of the kinds mentioned herein, capable of acting on the viscose without coagulating the latter. This term includes solutions of xanthates of cellulose and of cellulose derivatives.

I The expression strong mineral acids denotes sulphuric acid of at least 30 per cent. of H2804,

preferably at least 45 per cent. of H2804, and as regards the other mineral acids, solution of I equivalent strength.

The expression strong sulphuric acid orsulphuric acid containing at least about 30 per cent.

of sulphuric acid monohydrate denotes sulphuric acid having a content of 30 to 98 per cent. of

H2SO4. v

What Iblaim is:

1. A treatment of textile material which comprises converting a solution containing a dissolved cellulosic material into'a lather, and applying said lather to a textile material.

2. A treatment of textile material which comprises applying thereto a' lather of a solution of a cellulosic material and treating the material so as to convert the soluble cellulosi'c material into an insoluble c'ellulosic material while bonded to said, textile material.

3. A treatment of textile material, which comprises transforming asolution of a cellulosic material into a lather, applying the lather to the textile -material, and regenerating an insoluble cellulosic-material from said solution in a highly porous state. r

4'. A treatment as claimed in claim 1 wherein the original cellulosic solution is a solution containing a cellulosederivative.

solution to be transformed into lather, is asolution of'an alkali-soluble cellulosic material.

6; A process as claimed in claim 1, wherein of the compound of cellulose is viscose.

7. A process as claimed in claimv 1, wherein the compound of cellulose is a xanthate of a cellulose derivative. Q

8.; A treatmentas claimed in claim 1, wherein the transformation of thesolution containing a soluble cellulosic material, into a lather is effected with the aid of suitable mechanical means.

9. A treatment as claimed in claim 1, wherein the transformation of the solution into lather is effected with the aid of at least one substance having lather forming properties.

10. A treatment as claimed in claim 1, wherein the transformation of the solution into lather is efiected with the aid of atleast one substance having lather-forming properties, in combination with suitable mechanical means.

11. A treatment as claimed in claim 1, wherein soap is present to assist the formation of the lather.

12. A treatment as claimed in claim 1, wherein the solution is transformed into a lather, in the presence of a body belonging to the group of saponins.

13. A treatment of textile material which comprises applying to the textile material a lather produced of a solution of an alkali-soluble cellulosic material and then treating the material with an agent having a coagulating effect on the lather applied to the textile material and a. plasticizing effect on the freshly coagulated lather.

14. A treatment of textile material which comprises applying to the textile material, a lather produced of a solution containing a dissolved. alkali-soluble cellulosic material and then treat-- ing the material first with an agent which has a coagulating effectv on the lather'applied to the textile fibre and then with an agent which has a plasticizing effect on the freshly coagulated cellulosic material from said lather.

15. A process which comprises treatinga lather while intimately associated with'a textile fabric,

which lather contains a solution containing a dissolved cellulosic material, with an acid solution which is capable of regenerating an insoluble cellulosic material from said solution.

16. A process which comprises treating a lather in a preshaped state, which lather contains a solution of a cellulosic material, with an acid solution which is capable of regenerating an insoluble cellulosic material from said solution.

17. Textile material, carrying intimately bonded thereto, an insoluble cellulosic material which has' been produced by impregnating a textile material with a lather containing a dissolved cellulosic material and regenerating an insoluble cellulosic material from said dissolved cellulosic material, said product having a warm feel and being of a downy character.

18. A process of dressing or sizing a textile material which comprises applying a lather containing as a constituent, a dissolved cellulosic body, to said textile material, forcing the substance of the lather into the body of the textile material to impregnate the same, and thereafter treating the so impregnated textile material with an agency capable of coagulating a cellulosic substance in said textile material.

19. The herein described process of sizing textile material which comprises converting a solution containing a dissolved cellulosic body into the state of a lather, impregnating a textile material therewith, and. converting the dissolved cellulosic body into an undissolved cellulosic body which is insoluble in water.

LEON LILIENFELD. 

